EP0066189B1 - A process for preparing tetrakis (3-(3,5-dibutyl-4-hydroxyphenyl)propionyloxymethyl)methane - Google Patents

A process for preparing tetrakis (3-(3,5-dibutyl-4-hydroxyphenyl)propionyloxymethyl)methane Download PDF

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EP0066189B1
EP0066189B1 EP19820104369 EP82104369A EP0066189B1 EP 0066189 B1 EP0066189 B1 EP 0066189B1 EP 19820104369 EP19820104369 EP 19820104369 EP 82104369 A EP82104369 A EP 82104369A EP 0066189 B1 EP0066189 B1 EP 0066189B1
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process
reaction
step
mol
ester exchange
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EP19820104369
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German (de)
French (fr)
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EP0066189A1 (en
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Toru Yamanaka
Tadatoshi Yoshimura
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Mitsui Petrochemical Industries Ltd
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Mitsui Petrochemical Industries Ltd
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/03Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group

Description

  • The present invention relates to a process for preparing tetrakis [3-(3,5-dibutyl-4-hydroxyphenyl) propionyloxymethyl] methane.
  • Tetrakis [3-(3,5 dibutyl-4-hydroxyphenyl)-propionyloxymethyl] methanes having the general formula-
    Figure imgb0001
    wherein Bu is an n-, sec.-, iso-, or tert.-butyl group, are preferably used as stabilizers for rubbers, plastics, and other various polymers.
  • It is known that compounds having General Formula I are prepared by the steps of-
    • (A) reacting an alkyl acrylate having the general formula-CH2 = CH - COOR1 (II) wherein R' is an alkyl group having 1 to 4 carbon atoms, with 2,6-dibutylphenol, thereby forming a propionic acid ester having the general formula-
      Figure imgb0002
      wherein Bu and R' are the same as defined above; and
    • (B) effecting an ester exchange reaction between the propionic acid ester having the General Formula III and pentaerythritol without isolating said propionic acid ester (see US Patent No. 4085132).
  • This process is practically advantageous in that the isolation and purification operations of the intermediate product I from the reaction product at step A can be omitted and the catalyst used at the step A can be reused at the subsequent step B as is, since isolation of the ester I is not necessary. However, this process is disadvantageous in that by-products formed together with the desired intermediate product III at step A are also subjected to the ester exchange reaction with pentaerythritol at step B and these by-products and the ester exchange reaction products thereof are included in the desired final product I as impurities, these being difficult to separate from the desired final product I.
  • In order to solve these disadvantages, is has been proposed in Japanese Patent Application Laid-Open (Kokai) No. 56-12341 that the reaction temperature and the mol ratio of the alkyl acrylate II to the 2,6-dibutylphenol at step A be limited to specific ranges, thereby decreasing the production amounts of the undesired by-products at step A and improving the purity of the desired final product I.
  • The object of the present invention is to provide a process for preparing tetrakis [3-(3,5-dibutyl-4-hydroxyphenyl)propionyloxymethyl]methane in which the amount of the undesired by-products or impurities is remarkably decreased.
  • Another object of the present invention is to provide a process for preparing tetrakis [3- (3,5-dibutyl-4-hydroxyphenyl) propionyloxymethyl] - methane at an improved yield, purity, and whiteness without having to isolate the intermediate ester III, as compared with the process disclosed in Japanese Patent Application Laid-Open No. 56-12341.
  • Other objects and advantages of the present invention will be apparent from the following description.
  • In accordance with the first embodiment of the present invention, there is provided a process for preparing tetrakis [3-(3,5-dibutyl-4-hydroxyphenyl)propionyloxymethyl]methane, wherein an ester exchange reaction between a propionic acid ester having the general formula-
    Figure imgb0003
    wherein in Bu is an n-, sec.-, iso-, or tert.-butyl group and R1 is an alkyl group having 1 to 4 carbon atoms, and pentaerythritol in the presence of an alkaline catalyst is effected by adding 0.2 through 1.8 mol of water based on 1 mol of the alkaline catalyst before the substantial completion of the ester exchange reaction. This ester exchange reaction is referred to as the reaction of step B or step B herein.
  • In accordance with the second embodiment of the present invention, there is also provided a process for preparing tetrakis [3-(3,5-dibutyl-4-hydroxyphenyl) propionyloxymethyl] methane comprising the steps of-
    • (A) reacting an alkyl acrylate having the general formula-CH2 = CH - COOR1 wherein R1 is an alkyl group having 1 to 4 carbon atoms, with 2,6-dibutylphenol in the presence of an alkaline catalyst, thereby forming a reaction product containing a propionic acid ester having the general formula-
      Figure imgb0004
      wherein Bu is an n-, sec.-, iso-, or tert.-butyl group, and R' is the same as defined above, and distilling off the unreacted starting materials from the reaction product; and
    • (B) effecting an ester exchange reaction of the resultant reaction product and pentaerythritol by adding 0.2 through 1.8 mol of water based on 1 mol of the alkaline catalyst between the completion of the addition reaction of step A and the substantial completion of the ester exchange reaction.
  • According to the present invention, the addition of the specified amount of water at step B remarkably decreases the amount of undesired impurities produced, these impurities believed to be the addition products of the intermediate ester III to the desired product I. Thus, the purity of the desired product is remarkably increased. Furthermore, the addition of the specified amount of water at step B increases the reaction yield and the whiteness of the desired product, especially the transmittance at a wavelength of 425 nm.
  • The alkyl acrylate II is first reacted with 2,6-dibutylphenol, in the presence of the alkaline catalyst in a solvent at step A of the present invention, thereby forming the propionic acid ester having the above-mentioned General Formula III.
  • Examples of the alkyl acrylates II usable in the present invention are methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate. Methyl acrylate is most desirably used in the present invention.
  • Examples of the 2,6-dibutylphenols usable in the present invention are 2,6-di-tert.-butylphenol, 2 ,6-di-sec.-butylphenol, and 2,6-diisobutyl- phenol. Of these 2,6-dibutylphenols, 2,6-di-tert.-butylphenol is most desirably used in the present invention.
  • The mol ratio of the alkyl acrylate to the 2,6-dibutylphenol at step A can be varied within a wide range without affecting the desired advantages of the present invention. The recommendable mol ratio of the alkyl acrylate to the 2,6-dibutylphenol is within the range of from about 0.80 to about 1.07.
  • The alkaline catalysts usable in the present invention include, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, lithium aluminium hydride, sodium boron hydride, lithium hydride, sodium t-butoxide, potassium t-butoxide, sodium methoxide, potassium methoxide, sodium metal, and lithium metal. Especially desirable alkaline catalysts are the alcoxides of alkali metals such as sodium t-butoxide, potassium t-butoxide, sodium methoxide, and potassium methoxide. These alkaline catalysts are generally used in an amount of 0.5 through 8.0% by weight, desirably 1.0 through 5.0% by weight, based on the weight of the starting 2,6-dibutylphenol.
  • The addition reaction of step A of the present process can be carried out either in the presence of or in the absence of a solvent, although the use of a solvent is desirable. Examples of the solvents usable at step A of the present invention are dimethylformamide, dimethylacetamide, dimethylsulfoxide, hexamethylphosphoamide, acetonitrile, propionitrile, sulfonitrile, sulfolane, diglyme, tetrahydrofuran, and t-butyl alcohol. Especially, t-butyl alcohol is desirably used in the present invention. These solvents can be used in an amount of 5 parts by weight or less, desirably about 0.1 through about 1 part by weight, based on 1 part by weight of the starting 2,6-dibutylphenol.
  • The reaction conditions of the addition reaction of step A of the present invention can be varied within wide ranges. For instance, the reaction temperature is generally about 70 through about 100° C, desirably about 80 through about 95° C. The reaction pressure can be either normal atmospheric pressure or an elevated pressure, desirably atmospheric pressure through 5 kg/ cm2G. The reaction time can be generally 2 through 10 h, desirably 6 through 8 h. The reaction is desirably carried out under stirring in any type of conventional reaction vessel provided with a stirrer.
  • After the addition reaction of step A is completed, the unreacted alkyl acrylate I is distilled off from the reaction product. Any conventional distillation method can be used. The resultant reaction product is directly used as the starting material at the subsequent step B of the second embodiment of the present invention. It should be, however, noted that the propionic acid ester having the General Formula III produced by any methods can be used as a starting material in the ester exchange reaction of the first embodiment of the present invention.
  • The resultant reaction product including the desired propionic acid ester III is reacted with pentaerythritol at step B of the present invention in the conventional manner. Thus, the desired tetrakis [3- (3,5-dibutyl-4-hydroxyphenyl) pro- pionyloximethyl] methane includes tetrakis [3-(3,5-di-tert.-butyl-4-hydroxyphenyl)propionyloxymethyl] methane, tetrakis [3-(3,5-di-sec.- butyl-4-hydroxyphenyl)propionyloxymethyl] - methane, and tetrakis [3-(3,5-diisobutyl-4-hydroxyphenytl)propionyloxymethyi] methane. Tetrakis [3-(3,5-di-tert.-butyl-4-hydroxyphenyl)propionyloxymethyl]methane is especially desirably prepared by the present invention.
  • The mol ratio of the pentaerythritol to the intermediate propionic acid ester III is generally 1/4 through 1/5, desirably 1/4.2 through 1/4.6, although the ester exchange reaction of the present invention is not limited to these ranges.
  • The ester exchange reaction of step B of the present invention proceeds in such a manner that the ester group of the intermediate propionic acid ester I is reacted with the hydroxide groups of the pentaerythritol to form an alcohol such as methanol. This ester exchange reaction can be catalyzed by any catalyst conventionally used in the ordinary ester exchange reaction. Such catalysts are those usable at step A of the second embodiment of the present invention mentioned hereinabove. These alkaline catalysts are generally used in an amount of 0.4 through 8.0% by weight, desirably 0.8 through 5.0% by weight, based on the weight of the propionic acid ester I I However, in the second embodiment of the present invention, the alkaline catalysts used in the previous step A of the present invention and still contained in the resultant product of step A can be desirably used at step B of the present invention. Furthermore, the amount of the catalyst remaining in the resultant reaction product of step A of the present invention is sufficient to catalyze the ester exchange reaction of step B of the present invention and, therefore, no further addition of the catalyst at step B is required.
  • The ester exchange reaction of step B is desirably carried out in a solvent. The solvents used at step A of the present invention can also be used in the reaction of step B. Of course, the solvent or another solvent can be optionally added to the reaction mixture at step B in cases that the solvent is removed together with the unreacted alkyl acrylate at the distillation step.
  • The term the substantial completion of the ester exchange reaction used herein means such a condition that no substantial change, within analytical error, is observed in the yield of the desired product I when the ester exchange reaction is continued for a further 2 h. The ester exchange reaction is generally carried out at a temperature of about 80 through about 140° C under reduced pressure for about 5 through 10 h, although the present invention is not limited to these conditions.
  • According to the present invention, 0.2 through 1.8 mol, desirably 0.5 through 1.5 mol, of water based on 1 mol of the alkaline catalyst should be added at step B of the present invention. The water can be added to the reaction mixture at any time by the substantial completion of the ester exchange reaction in the first embodiment of the present invention or between the completion of the addition reaction of step A and the substantial completion of the ester exchange reaction of step B in the second embodiment of the present invention. The water is desirably added at the time just before the addition of the pentaerythritol, at the same time as the addition of the pentaerythritol, or after the initiation of the ester exchange reaction by the addition of the pentaerythritol. It is especially recommended that the addition of water be started at the stage when the yield of the desired product I becomes approximately 70% or more, especially approximately 80 through 90%. Thus, the yield, purity, and whiteness of the desired product are remarkably improved. The water may be added all at once, continuously, or intermittently. Less than 0.2 mol of the water based on 1 mol of the alkaline catalyst does not result in the desired improvements in the purity and whiteness of the desired product I. Contrary to this, more than 1.8 mol of the water based on 1 mol of the alkaline catalyst decreases the yield of the desired product I, although the purity and whiteness are improved.
  • The alcohol such as methanol formed in the ester exchange reaction of step B is removed at any time during the reaction from the reaction mixture. The removal of the alcohol can be effected by any known manner, for example, by distilling off under a reduced pressure of about 5 through 50 mmHg.
  • The ester exchange reaction of step B can be carried out in any conventional reaction vessel. Especially, according to the present invention, the reaction vessel used at step A is directly used in the subsequent step B without withdrawing the reaction product of step A. The reaction vessels are desirably provided with, for example, stirring unit, a heating apparatus, an addition device and a distillation apparatus.
  • The desired reaction product I is isolated from the reaction mixture and purified. The isolation and purification is desirably carried out by means of a recrystallization method. Examples of the solvents usable in the recrystallization are hexane, cyclohexane, heptane, ethanol, isopropanol, n-propanol, isobutanol, sec.-butanol, and n-butanol. Especially, it is desirable that medium alcohols such as isopropanol, n-propanol, isobutanol, sec.-butanol or n-butanol are used as a solvent for recrystallization and the desired product I is crystallized as an adduct of the alcohols.
  • According to the isolation and purification operation by means of the recrystallization method, the desired product I contained in the reaction product of step B is advantageously recovered at a high yield and at a high purity.
  • As mentioned hereinabove, according to the present invention, the desired tetrakis [3-(3,5-dibutyl-4-hydroxyphenyl) propionyloxyphenyl]-methane having an improved purity and whiteness is prepared at an improved yield, without isolating the intermediate product III from the reaction product of the step A, by the addition of the specified catalytic amount of water during the ester exchange reaction of step B. Accordingly, the tetrakis [3-(3,5-dibutyl-4-hydroxyphenyl)-propionyloxyphenyl]methane thus obtained is suitable for use as stabilizers for rubbers and plastics, especially due to the improvement in the whiteness thereof.
  • The present invention now will be further illustrated by, but is by no means limited to, the following examples.
  • Example 1
  • 26 ml of tert.-butanol, 1.42 g of potassium tert.-butoxide, 93.25 g of 2,6-di-tert.-butylphenol a, and 39.69 g of methyl acrylate b (i.e. the mol ratio of the compounds b/a = 1.02) were added, under a nitrogen atmosphere, to a 500 ml 4-necked flask provided whit a stirrer, a reflux condenser, a thermometer, and a nitrogen feed pipe and were allowed to react at a temperature of 87° C for 8 h with stirring. The flask was reduced under a pressure of 30 mmHg, whereby the unreacted methyl acrylate was distilled off. Thereafter, the pressure was raised to atmospheric pressure by feeding nitrogen to the flask.
  • As a result of a gas chromatograph analysis of the reaction product obtained in the above-mentioned step A, it was observed that the desired intermediate product, 3-(3,5-di-tert.-butyl-4-hydroxyphenyl)methylpropionate was obtained at a yield of 96.5% based on the starting 2,6-di-tert.-butylphenol.
  • Thereafter, 13.37 g of pentaerythritol (corresponding to 1/4.4 mol of the 2,6-di-tert.-butylphenol), 50 g of dimethylformamide, and 0.22 g of water were added to the reaction mixture obtained above. The mixture was first stirred at a temperature of 87° C for 10 min and then allowed to react at a temperature of 90° C under a pressure of 30 mmHg for 1 h, while the formed methanol was distilled off. Then, the reaction mixture was allowed to stand at a temperature of 100 through 140° C under a pressure of 20 mmHg for 6 h, whereby the dimethylformamide was distilled off and the ester exchange reaction was completed.
  • Thereafter, nitrogen was introduced to the flask to return the pressure to atmospheric pressure and the reaction mixture was neutralized with glacial acetic acid. As a result of a gas chromatograph analysis of the reaction product obtained at step B, it was observed that the desired final product was obtained at a yield of 92.1% based on the pentaerythritol.
  • The resultant sticky solid was recrystallized from 90% isopropanol to crystallize the desired product as an addition product. The crystallized product was dried. Thus, 103.6 g of the white crystal having a purity of 98.3% and containing 0.32% by weight of an addition product of the intermediate ester III to the desired product I (i.e. by-product), which was determined at a UV radiation of 254 nm by means of a high velocity liquid chromatography utilizing a Zorbax Sil® (available from Shimadzu Corporation) column, was obtained.
  • 30 g of the crystal obtained above was dissolved in 100 ml of toluene. The transmittance of this solution at a wavelength of 425 nm was 96.1 %.
  • Examples 2 and 3, and Comparative Examples 1 and 2
  • Example 1 was repeated except that the addition amount of the water at step B was changed as shown in Table 1 below.
  • The results are shown in Table 1.
    Figure imgb0005
  • As is clear from the results shown in Table 1, the products obtained in Examples 1 to 3 according to the present invention have an improved purity and excellent whiteness as compared with that obtained in Comparative Example 1 in which no water was added. Furthermore, the yield of the desired product was low in Comparative Example 2 in which an excess amount of water was used.
  • Examples 4 and 5
  • Example 1 was repeated except that the mol ratio of the methyl acrylate to the 2,6-di-tert.-butylphenol at step A was changed to 0.90 and 0.96.
  • The results are shown in Table 2 below.
  • Examples 6 and 7
  • Example 5 was repeated except that the addition time of the water during step B was changed as shown in Table 3 below. The addition of the water was carried out all at once.
  • The results are shown in Table 3.
    Figure imgb0006

Claims (9)

1. A process for preparing tetrakis [3-(3,5-dibutyl-4-hydroxyphenyl)propionyloxymethyl] - methane, wherein an ester exchange reaction between a propionic acid ester having the general formula- -
Figure imgb0007
wherein Bu is an n-, sec.-, iso-, ortert.-butyl group and R1 is an alkyl group having 1 to 4 carbon atoms, and pentaerythritol in the presence of an alkaline catalyst is effected by adding 0.2 through 1.8 mol of water based on 1 mol of the alkaline catalyst before the substantial completion of the ester exchange reaction.
2. A process as claimed in Claim 1, wherein the reaction temperature is 80 through 140° C.
3. A process as claimed in Claim 1, wherein the mol ratio of the pentaerythritol to the propionic acid ester is 1 /4 through 1 /5.
4. A process for preparing tetrakis [3-(3,5-dibutyl-4-hydroxyphenyl) propionyloxymethyl] - methane, comprising the steps of-(A) reacting an alkyl acrylate having the general formula-
Figure imgb0008
wherein R1 is an alkyl group having 1 to 4 carbon atoms, with 2,6-dibutylphenol in the presence of an alkaline catalyst, thereby forming a reaction product containing a propionic acid ester having the general formula-
Figure imgb0009
wherein Bu is an n-, sec.-, iso-, ortert.-butyl group and R1 is the same as defined above, and distilling off the unreacted starting materials from the reaction product; and
(B) effecting an ester exchange reaction between the resultant reaction product and pentaerythritol by adding 0.2 through 1.8 mol of water based on 1 mol of the alkaline catalyst between the completion of the addition reaction of step (A) and the substantial completion of the ester exchange reaction.
5. A process as claimed in Claim 4, wherein the amount of the catalyst is 0.5 through 8.0% by weight based on 2,6-dibutylphenol.
6. A process as claimed in Claim 4, wherein the reaction temperature of step (A) is 70 through 100° C.
7. A process as claimed in Claim 4, wherein the reaction temperature of step (B) is 80 through 140° C.
8. A process as claimed in Claim 4, wherein the mol ratio of the alkyl acrylate to the 2,6-dibutylphenol is 0.80 through 1.07.
9. A process as claimed in Claim 4, wherein the mol ratio of the pentaerythritol to the propionic acid ester is 1 /4 through 1 /5.
EP19820104369 1981-05-28 1982-05-18 A process for preparing tetrakis (3-(3,5-dibutyl-4-hydroxyphenyl)propionyloxymethyl)methane Expired EP0066189B1 (en)

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JP80123/81 1981-05-28

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0151368A2 (en) * 1983-12-22 1985-08-14 Ciba-Geigy Ag Process for the preparation of a hydroxyphenylcarboxylic-acid ester
WO1989005789A1 (en) * 1987-12-14 1989-06-29 Nauchno-Issledovatelsky Institut Khimikatov Dlya P Method of extracting pentaerythryl-tetrakis-[3-(3,5-ditert. butyl-4-oxyphenyl)propionate] from the reaction mass obtained during synthesis of said product
EP0437187A2 (en) * 1990-01-11 1991-07-17 Ciba-Geigy Ag Process for the preparation of esters of hydroxyphenylpropanoic acid
US5206414A (en) * 1990-01-11 1993-04-27 Ciba-Geigy Corporation Process for the preparation of hydroxyphenylpropionic acid esters

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US4683326A (en) * 1985-07-19 1987-07-28 Ciba-Geigy Corporation Solvent-free crystallization of pentaerythritol tetrakis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and the novel alpha-crystalline form thereof
JPH0657676B2 (en) * 1986-04-30 1994-08-03 ムサシノガイギ−株式会社 Independent particulate β crystal tetrakis- [3- (3,5-di -t- butyl-4-hydroxyphenyl) propionyloxymethyl] methane, and a manufacturing method thereof
US4883902A (en) * 1987-02-03 1989-11-28 Yoshitomi Pharmaceutical Industries, Ltd. Method of producing tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxymethyl]methane
JPH0710807B2 (en) * 1987-02-03 1995-02-08 吉富製薬株式会社 Tetrakis [3- (3,5-di-tertiary-butyl-4-hydroxyphenyl) propionyloxymethyl] The method of producing methane
DE68911436T2 (en) * 1988-09-07 1994-06-09 Yoshitomi Pharmaceutical Individual particles crystals in the form of alpha-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] methane and process for its preparation.
US5089656A (en) * 1990-07-18 1992-02-18 Himont Incorporated Process for the preparation of aryl-substituted propionic acid esters
US5136082A (en) * 1990-08-03 1992-08-04 Himont Incorporated Process for preparing organic esters and amides and catalyst system therefor
US5264612A (en) * 1992-09-28 1993-11-23 Himont Incorporated Process for the preparation of aryl-substituted propionic acid esters
US5498751A (en) * 1993-09-03 1996-03-12 Cps Chemical Company, Inc. Organotin catalyzed transesterification
US5606103A (en) * 1993-09-03 1997-02-25 Cps Chemical Company, Inc. Organotin catalyzed transesterification
WO2004048312A1 (en) * 2002-11-26 2004-06-10 Ciba Specialty Chemicals Holding Inc. Phenolic antioxidants in crystalline form
GB0324964D0 (en) * 2003-10-27 2003-11-26 Great Lakes Chemical Europ Preparation of hydroxyphenyl carboxylic acid esters
KR101189589B1 (en) * 2004-07-27 2012-10-12 시바 홀딩 인코포레이티드 Process for preparing solid particles of phenolic antioxidants
DE102009060420A1 (en) 2009-12-22 2011-06-30 Kowall, Fredy Norbert, 39291 Redundant selective contact-free direct drive for linear and rotary axes of large lathes, is provided with linear motors having four folds
CN101967081B (en) * 2010-10-15 2013-05-15 湖北恒鑫化工有限公司 Process for recovering water-containing methanol solution produced in production of antioxygen 1010
CN104230705A (en) * 2013-06-08 2014-12-24 中国石油化工股份有限公司 Preparation method for pentaerythritol tetracarboxylate

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FR2212323B1 (en) * 1972-12-27 1977-08-12 Ciba Geigy Ag
US4085132A (en) * 1975-06-24 1978-04-18 Ciba-Geigy Corporation Process for the production of hydroxyalkylphenyl derivatives
JPH0321537B2 (en) * 1979-07-10 1991-03-22 Mitsui Petrochemical Ind

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0151368A2 (en) * 1983-12-22 1985-08-14 Ciba-Geigy Ag Process for the preparation of a hydroxyphenylcarboxylic-acid ester
EP0151368A3 (en) * 1983-12-22 1986-05-07 Ciba-Geigy Ag Process for the preparation of a hydroxyphenylcarboxylic-acid ester
WO1989005789A1 (en) * 1987-12-14 1989-06-29 Nauchno-Issledovatelsky Institut Khimikatov Dlya P Method of extracting pentaerythryl-tetrakis-[3-(3,5-ditert. butyl-4-oxyphenyl)propionate] from the reaction mass obtained during synthesis of said product
EP0437187A2 (en) * 1990-01-11 1991-07-17 Ciba-Geigy Ag Process for the preparation of esters of hydroxyphenylpropanoic acid
EP0437187A3 (en) * 1990-01-11 1992-07-15 Ciba-Geigy Ag Process for the preparation of esters of hydroxyphenylpropanoic acid
US5206414A (en) * 1990-01-11 1993-04-27 Ciba-Geigy Corporation Process for the preparation of hydroxyphenylpropionic acid esters

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DE3260497D1 (en) 1984-09-06
CA1177092A (en) 1984-10-30
JPS57197245A (en) 1982-12-03
US4547585A (en) 1985-10-15
JPS619931B2 (en) 1986-03-27
EP0066189A1 (en) 1982-12-08
CA1177092A1 (en)

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